JPS62250453A - Production of lithographic printing plate - Google Patents

Abstract

PURPOSE:To obtain an image part having high resolving power and high sensitivity and a stain-free non-image area by coating a support with a layer contg. microcapsules contg. a photopolymerizable monomer and/or a photosensitive resin and by subjecting the coated surface to patternwise exposure and heating. CONSTITUTION:An original plate for lithography formed by coating a support with a layer contg. microcapsules is patternwise exposed with a metallic halide lamp or the like through a positive original plate superposed on the original plate for lithography. The microcapsules present in the exposed part, that is, the non-image area are hardened and the thermal softening temp. rises. The microcapsules present in the unexposed part, that is, the printing area undergoes no change in the thermal softening temp. The patternwise exposed original plate is then heated to a temp. between the thermal softening temp. of the unhardened microcapsules and that of the hardened microcapsules to soften only the microcapsules present in the printing area. By the softening, the walls of the microcapsules and/or the contents such as a photopolymerizable monomer and a photosensitive resin mix and form a lipophilic uniform film which ensures ink receptivity.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a method for manufacturing a lithographic printing plate, and more particularly to a method for manufacturing a lithographic printing plate by dry processing.

[Conventional technology]

Currently, the general method for manufacturing lithographic printing plates is to use a grained hydrophilic aluminum support, for example, in the case of a positive printing plate.
Apply 0-quinonediazide compound and phenol resin,
After pattern exposure, the photosensitive layer in the exposed area is eluted with an alkaline developer, washed with water, and the surface of the aluminum support in the area from which the photosensitive layer has been removed is exposed to air, which reduces its hydrophilicity. The process consists of applying gum arabic, etc., to prevent this from happening.

In the above-mentioned method, a lot of time is required for running after pattern exposure, and in addition to an automatic developing machine, a work area such as a gum coater, a developer, a gum solution, and a sink is also required. Furthermore, during development, in order to keep the remaining pattern area constant, complicated management such as proper developer temperature, development time, developer replenishment, and replacement is required. Additionally, there is a risk of pollution due to discharge of the developer and a risk of injury when handling the developer.

Also, a lot of time is required for cleaning and maintenance of the automatic developing machine and gum coater.

As described above, the conventional lithographic printing plate manufacturing process has many problems in the process after pattern exposure.

For this reason, a method for manufacturing a lithographic printing plate has been considered in which a pattern can be formed by a simple dry process after pattern exposure.

U.S. Pat. No. 3,374,094 states that 1) N-
vinylamine, 2) halogenated hydrocarbon, 3) P%B
A layer in which a triaryl compound of 1.5 bSAs is dispersed in a hydrophilic binder is provided on a support and a lithographic printing original plate is pattern-exposed to make the exposed area oil-sensitive, and then heated to vaporize the polymerization initiator 2) and fix it. A method is disclosed.

Further, U.S. Pat. No. 3,505,371 discloses that a lithographic printing original plate having l) a vinyl resin, and b) a polyene, a polythiol, and a polymerization accelerator provided on a support is heated after pattern exposure to melt the resin. , discloses a method of making exposed areas oil-sensitive and non-exposed areas hydrophilic. In all of these methods, the oil sensitivity of the image area and the hydrophilicity of the non-image area are insufficient, and it is difficult to obtain prints with high ink density that are completely free of stains. JP-A-58-224753 discloses that a lithographic printing original plate is coated with a layer containing photocurable microcapsules mainly containing a photocurable resin on a water-resistant support, subjected to pattern exposure, and then pressurized. A method is disclosed in which the entire surface is exposed again to make the exposed area oil-sensitive and the unexposed area hydrophilic.

This method requires a large pressurizing device to destroy the microcapsules by applying pressure, and in order to destroy the microcapsules with a practical pressurizing device, the diameter of the microcapsules must be several microns or more. This is necessary, and as the diameter of the microcapsules increases, the resolution of the pattern decreases. Additionally, there is a risk that the microcapsules may be destroyed during handling, causing stains.

[Problem that the invention seeks to solve]

Accordingly, an object of the present invention is to provide a method for producing a lithographic printing plate that provides high resolution, highly oil-sensitive image areas and stain-free non-image areas through a simple dry process.

[Means for solving problems]

The object of the present invention is to apply a layer containing microcapsules containing a photopolymerizable monomer and/or a photosensitive resin onto a support, subject the coated layer surface to pattern exposure, and then heat it. This is achieved by the method of manufacturing lithographic printing plates.

The process for producing the lithographic printing plate of the present invention involves heating the unexposed areas of the microcapsule wall, which has heat-softening property, and/or the inclusions such as photopolymerizable monomers and photosensitive resins in the microcapsules to mix together to create a homogeneous lipophilic plate. It utilizes the creation of a membrane.

The microcapsules mainly containing the photopolymerizable monomer and/or photosensitive resin used in the present invention are microcapsules whose thermal properties can be controlled by light, and are stable during normal handling and under normal conditions, but depend on the material. It has a thermal softening temperature and thermal transmission coefficient. When exposed to light, the microcapsules harden and their heat softening temperature increases significantly. When a positive original plate is overlaid on a lithographic printing original plate with microcapsules having these properties on a support and exposed in a pattern using a metal halide lamp, the microcapsules present in the exposed area, that is, the non-image area, harden and are exposed to heat. Softening temperature increases. On the other hand, the thermal softening temperature of the microcapsules present in the unexposed area, that is, the image area does not change at all.

Therefore, after pattern exposure, when heated to a temperature higher than the thermal softening temperature of uncured microcapsules and lower than the thermal softening temperature of hardened microcapsules, only the microcapsules existing in the image area are softened, and the microcapsule walls and/or The photopolymerizable monomer, photosensitive resin, and other inclusions in the microcapsules mix to form a lipophilic uniform film that is ink receptive. It is also possible to apply pressure with a roll or the like during heating to make it easier to mix the photopolymerizable monomer and photosensitive resin inclusions in the microcapsule walls and/or in the microcapsules. An image area strong enough to withstand printing can be created by heating alone, but in order to further increase the film strength and stiffness resistance, the entire surface can be exposed again.

The method for manufacturing the lithographic printing plate of the present invention is to create an image consisting of a lipophilic uniform film by heating after pattern exposure, and the particle size of the microcapsules used is smaller than that of the microcapsules normally used for pressure destruction. Since it can be made significantly smaller, it has the excellent feature of producing high-resolution lithographic printing plates that can faithfully reproduce pattern details.

The polymerizable monomer referred to in the present invention is a compound having one or more vinyl or vinylidene groups, preferably a plurality of vinyl or vinylidene groups, such as an acryloyl group, a methacryloyl group, an allyl group,
Examples include compounds containing unsaturated polyester groups, vinyloxy groups, acrylamide groups, etc. The most typical examples include reaction products of polyols, polyamines, amino alcohols, etc. and unsaturated carboxylic acids, and reaction products of acrylates or methacrylates having hydroxyl groups and polyisocyanates.

For example, typical compounds include polyethylene glycol diacrylate, propylene glycol dimethacrylate, pentaerythritol triacrylate, trimethylolpropane diacrylate, trimethylolpropane triacrylate, penquerythritol tetraacrylate, hexanediol diacrylate, 1.2
-Butanediol diacrylate, tetrakis β-acryloxyethylethylene diamine, reaction product of epoxy resin and acrylic acid, reaction product of methacrylic acid, pentaerythritol and acrylic acid, condensation product of maleic acid, diethylene glycol and acrylic acid, methyl methacrylate , butyl methacrylate, styrene, divinylbenzene, diarylnaphthalene, etc. Regarding these monomers, see JP-A-49-52889 and JP-A-48-686.
No. 41, No. 48-32586, Special Publication No. 49-7115
You can also choose from those disclosed in the issue. A plurality of these can be used in combination depending on the purpose.

These monomers usually absorb in the ultraviolet region of 300 nm or less, so in order to impart photosensitivity to ultraviolet to visible light sources, a photosensitive substance that absorbs ultraviolet to visible light and polymerizes the monomer is used in combination. is desirable. An example of such a photopolymerization initiator is what is generally known as a photopolymerization initiator.
John Wil
ey & 5ons), Yakuka et al., “Photosensitive Resin,” Nikkan Kogyo Shimbun, Tsunoda et al., “Photosensitive Resin,” Society of Printing, etc.

Specific examples of photopolymerization initiators include aromatic ketones, quinone compounds, ether compounds, and nitro compounds.

Specifically, benzoquinone, phenanthrenequinone, naphthoquinone, diisopropylphenanthrenequinone, benzoisobutyl ether, benzoin, furoinbutyl ether, Michler's ketone, Michler's thioketone, tetraphenyllophine dimer, fluorenone, trinitrofluorenone, β-benzoyl. Contains aminonaphthalene.

These are added in an amount of about 0.1% to 30% based on the vinyl compound.

Furthermore, in order to efficiently perform curing by photopolymerization, a patent application was filed in 1983.
Polymers described in Japanese Patent Publication No. 0-151864, Japanese Patent Publication No. 46-32714, and Japanese Patent Publication No. 49-34041 can be contained in microcapsules.

When encapsulating the above polymerizable monomer 1 photopolymerization initiator, photosensitive resin, etc., a solvent can be used in combination. As the solvent, natural or synthetic oils can be used alone or in combination. Examples of solvents include cottonseed oil, kerosene, aliphatic ketones, aliphatic esters, paraffins, naphthenic oils, alkylated biphenyls, alkylated terphenyls, chlorinated paraffins, alkylated naphthalenes, ■-phenyl-1-1silylethane, 1- Diarylethanes such as phenyl-1-p-ethyl phenylethane, 1.1'-'; tolylethane, and the like can be mentioned.

Examples of photosensitive resins include cinnamate esters of polyvinyl alcohol, photosensitive resins made of azide compounds and cyclized rubber, or styrene-butadiene copolymers, diazo photosensitive resins, and photosensitive resins made of polyvinylacetophenone and benzaldehyde. etc.

In addition to the above, a thermal polymerization inhibitor may be added. For example, hydroquinone, p-methoxyphenol, di-t-butyl-p-cresol, pyrogallol, t-butylcatechol, pentuquinone, 4,4'-thiobis(
3-methyl-6-t-butylphenol), 2.2'
-methylenebis(4-methyl-6-t-butylphenol), 2-mercaptobenzimidazole, and the like are useful.

Further, for the purpose of coloring the photosensitive layer, a dye or a pigment, a pH indicator as a print-out agent, or a dye described in JP-A-60-120354 can be contained in the microcapsules.

In addition, in order to color the image area, at least one of a photocurable microcapsule color former or a color developer that produces a colored substance upon contact with the color former can be included. A coloring agent is one that has the property of producing color by donating electrons or accepting protons such as acids, and is usually colorless and includes, but is not limited to, lactones, lactams, sultones, spiropyrans, esters, etc. A compound having a partial skeleton such as an amide and whose partial skeleton opens or cleaves upon contact with a color developer is used. Specific examples include crystal violet lactone, benzoylleucomethylene blue, malachite green lactone, rhodamine β-lactam, and 1°3.3-)dimethyl-6'-ethyl-81-butoxyindolinobenzospiropyran.

As color developers for these color formers, phenol compounds, organic acids or metal salts thereof, oxybenzoic acid esters, clays, etc. are used.

In particular, the melting point is 50@~250°C, particularly preferably 6
Phenols and organic acids that are sparingly soluble in water at a temperature of 0'' to 200°C are desirable.

Examples of phenolic compounds include 4,4'-isopropylidene-diphenol (bisphenol A), p
-tert-butylphenol, 2,4-dinitrophenol, 3,4-dichlorophenol, 4,4'-methylene-bis(2,6-di-tert-butylphenol), p-phenylphenol, 4,4-cyclohexylphenol Cylidene diphenol, 2゜2'-methylenebis(4-
tert-butylphenol), 2,2'-methylenebis(α-phenyl-p-cresol)thiodiphenol, 4,4'-thiobis(5-tert-butyl-m
-cresol), sulfonyldiphenol, 1.1-bis(4-hydroxyphenyl)-n-dodecane, 4.4
-bis(4-hydroxyphenyl)-1-pentanoic acid ethyl ester, p-tert-butylphenol-formalin if compound, p-phenyl-phenol-formalin condensate, and the like.

Examples of organic acids include 3-tert-butylsalicylic acid, 3
, 5-tert-butylsalicylic acid, 5-α-methylbenzylsalicylic acid, 3.5-di-α-methylbenzylsalicylic acid, 3-tert-octylsalicylic acid, 5-
α,γ-dimethyl-α-phenyl-γ-7enylprobylsalicylic acid and the like are useful.

Examples of oxybenzoic acid esters include ethyl p-oxybenzoate, butyl p-oxybenzoate, heptyl p-oxybenzoate, and benzyl p-oxybenzoate.

Furthermore, a foaming agent can be included in the photocurable microcapsules in order to effectively mix the contents of the capsules by heating.

As the blowing agent, nitroso compounds, sulfohydrazide compounds which are hydrazine derivatives of organic sulfonic acids, hydrazo compounds and azo compounds can be used.

Specific examples of the organic blowing agent include nitroso-based compounds such as dinitrosopentamethylenetetramine, N,N'-dimethyl-N, N'-dinitrosoterephthalamide, and trinitron trimethylenetriamine.

Examples of sulfohydrazide compounds include p-)luenesulfohydrazide, benzenesulfohydracite, p, p'
-oxybis(benzenesulfohydrazide), benzene-1,3-disulfohydrazide, 3,3'-disulfohydrazide phenylsulfone, toluene-2,4-disulfohydrazide, p, p'-thiobis(benzenesulfohydrazide) Examples of the hydrazo compound include hydrazodiruboamide, N,N'-dibenzoylhydrazine, β-acetylphenylhydrazine, bayulia, 1,1-diphenylhydrazine, and the like.

Examples of the azo compound include azobisisobutyronitrile, azodicarbonamide (azobisformamide), diazoaminobenzene, azocarboxylic acid diethyl ester (diethyl azodicarboxylate), and the like.

All of these organic blowing agents decompose upon heating and generate nitrogen gas. Furthermore, some compounds generate some carbon monoxide, carbon dioxide, and water vapor in addition to nitrogen gas, but at least 60% of the generated gas is nitrogen gas. Also, the amount of gas generated is approximately 100 to 300 mβ
/g.

The thermal decomposition temperature of these organic blowing agents ranges from about 80°C to 300°C.
The temperature ranges up to about ℃.

A thermal decomposition aid can also be used in the present invention to lower the decomposition temperature of the organic blowing agent.

As thermal decomposition aids, urea and urea derivatives, zinc white,
Lead carbonate, lead stearate, glycolic acid, etc. are effective. Among these, urea and urea derivatives, such as ureaethanolamine, guanylurea, aminoguanidine carbonate, etc. are particularly preferred. The amount of the thermal decomposition aid added is preferably about 30 to 60% by weight based on the organic blowing agent.

For example, the decomposition temperature of pure chemical azodicarbonamide is said to be 230°C, but it can be lowered to about 120°C by adding various thermal decomposition aids.

The microcapsules used in the present invention can be produced by methods known in the art. For example, U.S. Patent No. 2,800.4
57, a method utilizing coacervation of a hydrophilic wall-forming material as seen in No. 2.800.458;
U.S. Patent No. 3.287.154, British Patent No. 990°443, Japanese Patent Publication No. 38-19574, No. 42-446
No. 42-711, interfacial polymerization methods, U.S. Pat.
No. 3, U.S. Pat.
．． 796.669, U.S. Patent No. 3.914.511
U.S. Pat. No. 4.001.140, U.S. Pat. No. 4.087.376
No. 4, No. 089.802, a method using a urea-formaldehyde-based or urea-formaldehyde-resorcinol-based wall forming material, U.S. Patent '44.0
25゜455, a method using wall forming materials such as melamine-formaldehyde resin, hydroxypropyl cellulose, etc., Japanese Patent Publication No. 36-9163, Japanese Patent Application Laid-open No. 1987-9
In 5it by polymerization of monomers found in No. 079
U method, British Patent No. 952.807, British Patent No. 965°07
Electrolytic dispersion cooling method as seen in U.S. Patent No. 4, U.S. Patent No. 3.111
, No. 407, and the spray drying method found in British Patent No. 930.422. Although not limited thereto, it is preferable to emulsify the core material and then form a polymer membrane as the microcapsule wall.

Specific examples of polymeric substances that form the microcapsule walls include polyurethane, polyurea, polyamide, polyester, polycarbonate, urea-formaldehyde resin,
Examples include melamine resin, polystyrene, styrene methacrylate copolymer, styrene-acrylate copolymer, gelatin, polyvinylpyrrolidone, polyvinyl alcohol, and the like.

Two or more types of polymeric substances can also be used in combination.

Preferred polymeric materials are polyurethane, polyurea, polyamide, polyester, polycarbonate, and more preferred are polyurethane and polyurea.

The particle size of the microcapsules is preferably adjusted to 30μ or less and 0.01μ or more, particularly preferably 10μ or less from the viewpoint of handling properties, and 5μ from the viewpoint of pattern resolution.
The following are particularly preferred.

When making capsules, water-soluble polymers and surfactants can be used.Water-soluble polymers include water-soluble anionic polymers, nonionic polymers, and amphoteric polymers. Both natural and synthetic compounds can be used, and examples thereof include those having a -COO-1SO3- group. Specific anionic natural polymers include gum arabic and alginic acid, while semi-synthetic products include carboxymethyl cellulose, phthalated gelatin, sulfated starch, sulfated cellulose, and lignin sulfonic acid.

Synthetic products include maleic anhydride-based (including hydrolyzed) copolymers, acrylic acid-based (including methacrylic acid-based) polymers and copolymers, vinylbenzenesulfonic acid-based polymers and copolymers, Examples include carboxy-modified polyvinyl alcohol.

Examples of amphoteric compounds include gelatin.

Examples of surfactants include nonionic surfactants such as polyoxyethylene alkyl ethers, polyoxyethylene alkyl phenyl ethers, polyoxyethylene fatty acid esters, sorgokun fatty acid esters, polyoxyethylene sorbicun fatty acid king esters, and glycerin fatty acid esters. Surfactants, such as fatty acid salts, alkyl sulfate ester salts, alkylbenzene sulfonate salts, alkylnaphthalene sulfonate salts, dialkyl sulfosuccinate ester salts, alkyl phosphate ester salts, naphthalene sulfonic acid formalin condensate, polyoxyethylene alkyl sulfate ester salts and cationic surfactants such as alkylamine salts, quaternary ammonium salts, polyoxyethylene alkylamine salts, and fluorine-based surfactants. These dispersion stabilizers may be used alone or in combination of two or more.

As the emulsifying device used for emulsifying and dispersing, one that applies a large shearing force to the processing liquid or one that applies high-intensity ultrasonic energy is suitable.

In particular, emulsifying devices having a colloid mill, a homogenizer, a capillary emulsifying device, a liquid siren, an electromagnetic strain ultrasonic generator, and a Pohlmann whistle can give good results.

Binders are used to coat the microcapsules and to impart hydrophilicity to the microcapsules. Binders can be used alone or in combination. This binder can be mainly hydrophilic. Typical hydrophilic binders are transparent or translucent hydrophilic binders, such as gelatin, gelatin derivatives, cellulose derivatives such as carboxymethyl cellulose and methyl cellulose, and natural substances such as starch, polysaccharides such as gum arabic, etc. Includes synthetic polymeric materials such as water-soluble polyvinyl compounds such as polyvinyl alcohol, polyvinylpyrrolidone, acrylamide polymers, polyacrylic acid, and vinyl acetate-acrylic acid copolymers.

The non-image area of the lithographic printing plate of the present invention can utilize the hydrophilicity of the hydrophilic capsule wall and/or the hydrophilic binder used, or can utilize the hydrophilicity of the hydrophilic support. Microcapsules on a hydrophilic support,
Particularly good results can be obtained when the hydrophilic binder is provided without strongly adhering the microcapsules photocured on a printing press, and the hydrophilicity of the hydrophilic support is exposed by removing the hydrophilic binder.

When a hydrophilic capsule wall or a hydrophilic binder is used as a non-image area, a melamine formaldehyde resin, urea formaldehyde resin, glyogysar, or other crosslinking agent can be added to the photosensitive solution.

Supports include paper, paper laminated with plastics (e.g., polyethylene, polypropylene, polystyrene, etc.), plates of metals such as aluminum (including aluminum alloys), zinc, iron, copper, etc., cellulose acetate, propion cellulose acid, cellulose butyrate, polyethylene terephthalate, polyethylene, polystyrene,
These include plastic films such as polypropylene, polycarbonate, polyvinyl acetal, etc., and paper or plastic films laminated or vapor-deposited with metals such as those mentioned above. These supports are subjected to surface treatments such as surface roughening treatment and surface hydrophilic treatment as necessary.

For example, an aluminum support is surface treated as follows. There is an electrochemical graining method in which an aluminum plate is grained by passing electricity through it in a hydrochloric acid or nitric acid electrolyte, a wire brush graining method in which the aluminum surface is scratched with a metal wire, and a polishing method to grain the aluminum surface using an abrasive agent. Mechanical graining methods such as the pole grain method, which uses a nylon brush and an abrasive to grain the surface, and the brush grain method, which uses a nylon brush and an abrasive to grain the surface, are used alone or in combination.

Thus, grained aluminum is chemically etched with acid or alkali.

When an acid is used as an etching agent, it takes a very long time to destroy the fine structure, which is disadvantageous in industrial application, but this can be improved by using an alkali as an etching agent.

Alkaline agents suitably used for these purposes include caustic soda, soda carbonate, sodium aluminate, sodium silicate,
Using sodium phosphate, potassium hydroxide, lithium hydroxide, etc., the preferred concentration and temperature ranges are 1 to 50% by weight and 20 to 100°C, respectively, and the dissolved amount of ^l is 5 to 20 g.
/m' is preferable.

After alkaline etching, acid washing is performed to remove the dirt (smut) remaining on the surface. The acids used include nitric acid, sulfuric acid, phosphoric acid, chromic acid, butic acid, and hydrofluoric acid.

In addition, for the smut removal treatment after the electrochemical surface roughening treatment, preferably 15 to 65% by weight at a temperature of 50 to 90°C as described in JP-A-53-12739.
and the alkali etching method described in Japanese Patent Publication No. 48-28123.

Although the aluminum plate treated as described above can be used, it is also possible to further perform treatments such as anodic oxidation coating treatment and chemical conversion treatment.

The anodic oxidation treatment can be performed by a method conventionally used in this field. Specifically, sulfuric acid, phosphoric acid,
When a direct or alternating current is passed through aluminum in an aqueous or non-aqueous solution containing chromic acid, oxalic acid, sulfamic acid, benzenesulfonic acid, etc. or a combination of two or more of these, an anodized film can be formed on the surface of the aluminum support. can.

The processing conditions for anodic oxidation vary depending on the electrolyte used and cannot be determined unconditionally, but generally the electrolyte concentration is 1 to 80% by weight, the solution temperature is 5 to 70°C, and the current density is 0. A range of .5 to 60 ampere/dm'', a voltage of 1 to 100 V, and an electrolysis time of 10 to 100 seconds is suitable.

Among these anodic oxidation coating treatments, the British Patent No. 1
．． No. 412.768, the method of anodizing at high current density in sulfuric acid, and the phosphoric acid electrolytic bath method described in U.S. Pat. No. 3,511,661. A method of anodic oxidation is preferred.

Anodized aluminum plates are further described in U.S. Patent No. 2.
'714.066 and '3.131.461, alkali metal silicates,
Hydrophilic cellulose containing water-soluble metal salts (e.g. zinc acetate), e.g. , carboxymethyl cellulose, etc.) may also be provided.

When coating on a support, fillers such as talc powder, glass powder, clay, starch, wheat flour, corn powder, Teflon powder, polyethylene powder, etc. may be added to improve vacuum adhesion during pattern baking. good.

In addition, the various additives, binders, antioxidants, dispersants, antifoaming agents, pigments, dyes, surfactants, coating methods, usage methods, etc. conventionally used in recording systems are well known (known, U.S. Patent No. 2.'711.375, U.S. Patent No. 3.
625.736, British Patent No. 1.232.347,
Disclosed in JP-A-50-44012, JP-A-50-50112, JP-A-50-127718, JP-A-50-30515, US Pat. No. 3.836.383, US Pat. No. 3.846.331, etc. You can use those methods.

Further, a protective layer or a matte layer may be provided to control the surface properties of the lithographic printing original plate.

The lithographic printing original plate prepared as described above is exposed to actinic light and then heated. Examples of active light sources include mercury lamps, metal halide lamps, xenon lamps, chemical lamps, and carbon arc lamps. Also, high-density energy beam (laser beam or electron beam)
Scanning exposure according to the method can also be used in the present invention. Examples of such laser beams include helium neon lasers, argon lasers, krypton ion lasers, helium cadmium lasers, and the like.

Heating devices used for heating include, for example, heating while contacting the photosensitive surface with a heat roller with a built-in heater, heating by contacting with a hot plate, heating sources such as ribbon heaters, sheathed heaters, infrared heaters, etc. Methods that directly heat the plate, such as placing it near the plate surface, blowing heated air, immersing it in heated liquid, or contacting it, and methods that generate self-heating by irradiating it with electron beams, high-frequency waves, or other electromagnetic waves are used. can.

The heating temperature and time are determined by the microcapsule wall material, wall thickness, photopolymerizable monomer, photosensitive resin, and other inclusions in the microcapsule, and are limited to specific values. 70℃~
A range of 300°C is effective, and a preferred range is 80°C to
The temperature is 250°C, more preferably in the range of 90°C to 220°C.

At temperatures below 70°C, it is difficult to obtain a uniform lipophilic film;
If the temperature is above ℃, there is a risk of staining. Heating time is 1
A range of 720 to 20 minutes is effective, but a preferred range is 1715 to 15 minutes, more preferably 1/10 to IO
It is a minute.

If pressurization is used in combination, this can be easily done by passing the material between two heated rolls with built-in heaters, or it can be done by passing it between two rolls immediately after heating or in the heating zone. Can be done. Although the applied pressure is not limited to a specific value, it is practically preferably about 500 kg/cd or less.

The lithographic printing plate obtained according to the present invention may be subjected to hydrophilic treatment in non-image areas or lipophilic treatment in image areas on the plate surface for the purpose of further improving printability. The treatment liquid used for hydrophilic treatment generally contains a hydrophilic resin such as gum arabic, a phosphate, an aluminum alum compound, and at least one acid, and a ferrocyan compound or a ferricyan compound. There are things that are the main subject. As a treatment liquid used for lipophilization treatment□
Examples include those mainly composed of polymers having parent wood groups or metal salts thereof.

〔Example〕

Examples of the present invention will be shown below, but the present invention is not limited thereto.

Example 1 (1) A support was produced as follows.

A substrate was produced by the method disclosed in Japanese Patent Application Laid-Open No. 56-28893. That is, the surface of an aluminum plate with a thickness of 0.24 mm was grained using a nylon brush and a 400 mesh water suspension of pumice stone, and then thoroughly cleaned with water. Then diluted with 10% sodium hydroxide at 70°C for 60 min.
After dipping for seconds and etching, washing with running water (20%)
It was neutralized and washed with INO, and then washed with water. The anode special voltage is 12. 1 using a sinusoidal alternating waveform current under the condition that the ratio of the cathode special electricity quantity to the anode electricity quantity is 0.8 at TV.
% nitric acid aqueous solution with an anode electricity amount of 160 chlorine/dm''.The surface roughness at this time was measured to be 0.6μ (Ra display). After immersion in 30% sulfuric acid and desmutting at 55°C for 2 minutes, the current density was 2 A at 76 m in 20% sulfuric acid.
It was anodized to a thickness of 2.7 g and 76 m''.Then, it was immersed in a 2.5% aqueous solution of sodium silicate at 70°C for 1 minute, then washed with water and dried.

(2) Next, a photosensitive solution was prepared as follows.

2.2-dimethoxy-2-phenylacetophenone 5g
was dissolved in 40 g of trimethylolpropane triacrylate, and then Takenate DllON (manufactured by Takeda Pharmaceutical @) was added.
Og was dissolved and mixed to form an oil phase.

This oil phase was mixed with 2% polyvinyl alcohol PVA-20.
5 (manufactured by Kuraray ■) was emulsified and dispersed in 50 g of an aqueous solution.While stirring this emulsion at room temperature, 1.67 g of diethylenetriamine was added.
% aqueous solution was added and the mixture was continuously stirred. After 30 minutes, the temperature was raised to 0°C, and after further stirring for 1 hour, it was cooled. The average particle size of the resulting microcapsules was 2.8μ.

(3) To 50 g of the microcapsule liquid thus obtained, 100 g of water and white dextrin (manufactured by Nippon Deka Chemical Co., Ltd.) Ig were added to obtain a photosensitive liquid. The coating material was coated on the aluminum support using coating rod #14 so that the coating weight after drying was 4.6 g/m'', and dried to obtain a lithographic printing original plate.

(4) Layer a positive film on this original printing plate, vacuum-adhere it, and apply ET 26 V UDNS UL manufactured by Nuark Co., Ltd.
TRA-PL[IS FLIP-TOP PLATE
! After exposure using JAKER, the plate was heated for 2 minutes in an air constant temperature bath at 160°C to obtain a lithographic printing plate.

(5) When this was attached to a Heidelberg G 7.0 type printing machine and printed, a clean print with excellent resolution was obtained.

Example 2 (1) A photosensitive solution was prepared as follows.

30 g of trimethylolpropane triacrylate, 2.
3 g of 2-dimethoxy-2-phenylacetophenone, 15 g of Burnock DN950 (manufactured by Dainippon Ink ■), and 20 g of ethylene dichloride were mixed to form an oil phase.

This oil phase was emulsified and dispersed in a 2% aqueous methylcellulose solution. While stirring this emulsion at room temperature, a 1.67% aqueous solution of diethylenetriamine was added.

g and continued stirring. After 30 minutes, the temperature was raised to 0°C, and after further stirring for 30 minutes, the mixture was cooled. The average particle size of the resulting microcapsules was 2.4μ.

(2) The thus obtained microcapsule liquid was coated in Example 1 so that the coating weight after drying was 4.2 g/m'.
A lithographic printing original plate was obtained by coating the aluminum support described in 1. and drying it.

(3) Layer a positive film on this printing original plate, vacuum-adhere it, and use Nuark's ET26VυDNS ULTRA.
-PLUS FLIP-TOP PLATE MA to E
After exposure from R2, the microcapsule was heated for 1 minute in an air constant temperature bath at 150° C., and then the entire surface of the microcapsule was exposed to light to obtain a lithographic printing plate.

(4) When this was installed on a Heidelberg G, T, O type printing machine and printed, a clean printed matter with excellent resolution was obtained.

Date 3, Showa, Relationship with the person making the amendment Applicant name (520) Fuji Photo Film Co., Ltd. 4, Agent 6, Subject of amendment Column for detailed explanation of the invention in the specification (1) Specification No. Change “70℃” in line 9 of page 28 to “60℃”
℃”, corrected.

(2) “80℃” in the same book, page 28, line 10, is changed to “70℃”
I am corrected.

(3) “90℃” in the same book, page 28, line 11, is changed to “80℃”
I am corrected.

(4) “70℃” in the same book, page 28, line 12, is changed to “60℃”
I am corrected.

Claims (1)

[Claims] A method for producing a lithographic printing plate, which comprises applying a layer containing microcapsules containing a photopolymerizable monomer and/or a photosensitive resin onto a support, subjecting the coated layer to pattern exposure, and then heating.